Lubricants



rmeaoetaaieis v 2,388,074" I l UNITED STATES, PATENT OFFIC gleam I rLUBRICANTS John A. Patterson and Bush l MoCleary. Mon,

N. Y,, anignorl to The flexal Company, New York, N. Y., a corporation ofDelaware No Drawing. Application mu 2 2, 1942, a vser|iu1so..4io,oiis

This invention relates to the use of metal derivatives oi compositionsobtained or derived from theAnacardium semis or .the Anacardiaceaeiamily in hydrocarbon oils,- particularly petroleum oils, to improve theproperties of the lubricants compounded therewith.-

The additive ingredients the present invention are prepared from theextracted oils obtained from the Anacardium genus of the Anacardiaceaeiamily and include the compositions and constituents oi such oils ascashew nut shell oil, markin nut shell oil, Japanese lac, etc. It

. is the consensus of the authorities on these extractedoils that thechemical compositions, thereof consist primarily oi! various types oiaromatic derivatives .such as ,an'acarjdic acid (CaaHazOa), cardel(831115204), cardanol {(6201-1120) anacardol (CiaHaoQ) anililnishlol(Czol i'soos) it has been discovered that the addition of smallquantities of an oil-soluble or oil-miscible metal derivative of theoil-soluble phenolic compositions contained in, or derlvedfrom theAnacardium genusoi the Anacardiaceae family-t0 a refined hydrocarbon oilprovides a lubricant or a compounding lubricant which possesses improvedresistance to sludge, varnish and lacquer formation in operation.

The phermllc compositions to which this inventlon applies are thoseoil-soluble phenols which. exist'in the naturally occurring Anacardl'unioils or are formed by the decomposition of other arematic derivativespresent in theoils. These oilsoluble phenols are. usually uroncorcli-hvdric phenols posseming; long chain unsaturated alhvi groupsattached to the nucleus. a

'The naturally, occurring cashew nut shell oil is described ascontaining approximately oov. anacardic acid and l ii% cardol. Neitherof. these constituents are applicable to. the present invention in thatauacardlc acid fraction con tains a carbonyl group and the cardolfraction, while described as a phenolic composition, is

in the commercial oil depends upon the degree of 1 heat used intheextraction process. Cardanol is an oil-soluble phenolic compositionwhich is,

icalof: 14" carbon atoms in the meta position. For] the purposes of thepresent invention, this phenolic composition may be obtained. from themlflclfid Oil by'fthe following methods: (1) dis- Claims. (dicta-s) atgreatly reduced pressure; (2) steam distilla tion of the commercialcashew nut shell oil at atmospheric or. reduced' pressure; (3)destructive distillation of the solvent extracted cashew n'ut shell oil;or (4) decarboxylation of the solvent extracted cashew nut shell oilwith subsequent distillation or solvent extraction.

Upon distillation of the commercial cashew nut shell oil, an oil-solubledistillate is obtained desired, this lower boiling fraction may beremovedby fractional distillation.

which consists almost entirelyoi' cardanol. The cardanol-distills' overas an oil-soluble, lightcolored liquid at approximately 225 C. and 10mm. Hg. This compound is very unstable and upon heating formscondensation andpolymerization products together with co-polymers.

In addition to the cardanol, the distillate obtained contains a lowerboiling traction possessing a nicotine-like odor which rapidly darkenswhen exposed to the atmosphere. This fraction, which amounts to about 5%of the original oil contains approximately (9.64% nitrogen. Ii

The following physical constants were obtained on two distillates oi.the commercially available thermal extracted cashew nut shell oil, onebeing obtained by vacuum distillation at 10 Bromine No 136 118' HydroxflNo '183 381 3% Neutral cation No 6 3. 5 Sapcnifleation No" ii. 4 Percentsulfur 0.10 ll. 10

.li'iZlG. mercury (A), and the other by steam dis-= tillation atatmospheric pressure (Bi.

The oil soluble or oll misclhie metal derivatives so of theseoil-soluble phenolic compositions may be incorporated in any refinedhydrocarbon oil which is normally subject to oxidation conditions duringservice. Among these hydrocarbon oils which may be improved are thepetroleum lubricating oils such as motor, Diesel, turbine and aviationoils, and the refinedvhydrccarbon oils used in the preparation ofindustrial lubricents, greases, textile oils, etc.

The particular metals which may he used to.

term the metal derivatives by the present inven tion include any of thefollowing metals: sodium, potassium, lithium; calcium, barium.strontium,

mium, lead, titanium, antimony; chromium,

' described as possessing an unsaturated'alkyl radmanganese, iron,cobalt, nickel and copper, with alkaline earth metals a preference givento the and tin and zinc:

present invention are verysusceptible to polyflllation oi the commercialcashew nut shell oil to merization and condensation reactions which resition.

sult in oil-insoluble products whose metal derivatives arealsooil-insoluble. It has been found that by partially hydrogenating theunsaturated alkyl radicals, these undesirable reactions are avoided andthe partially hydrogenated product .is sufliciently stable to proceedwith the formation of the metal derivatives thereof. These hydrogenationreactions do not completely hydrogenate the unsaturated alkyl radicaland a certain degree of unsaturation is left which may be utilizedinfurther improving the product by nitrogen and phosphorus.

One method of preparing the metal derivatives which simultaneouslyincludes the partial hydrogenation of the oil-soluble phenoliccomposition is the reaction of a solution of the desired metal in liquidammonia'with the phenol. This reaction results in a partialhydrogenation of the unsaturated constituents by means of the residualhydrogen displaced by the metal.

Other reactions may be used which, due to the the incorporation-ofvarious radicals containing i such inorganic constituents as sulfur,halogen,-

. toluene solution of low temperatures of operation, do not require astabilization step in order to avoid the polymerization reactions of thetions. Such a method is a reaction of thesolution of a metal salt'suchasthe halide in' liquid ammonia with the oil-soluble phenolic compo- Theinvention is not limited to these particular methods of preparing themetal derivatives and any other classical method may be used which willresult in the formation oi' oil-soluble ,or oilmiscible' metalderivatives. V

It is to be. understood that the term metal derivative ofthe'oil-soluble phenolic composi-' tions derived from a member of theAnacardium genus of the Anacardiaceae family? as appearing throughoutthe specification and-claims, unless otherwise stated, includes themetal derivatives,

phenolic composithat is the partially or completely neutralized hydroxylgroups of the oil-soluble phenols contained in or derived from theAnacardium genus of the Anacardiaceae family and including cashew nutshell oil,. marking nut shell oil, Japanese lac, etc., together with thehydrogenated derivatives and/or further derivatives thereof contain ngsulfur, halogen, nitrogen and phosphorus radicals which have heretoforebeen known to impart-improving qualities.

of! and the residual toluene Emample 1 415 gramsof cardanol'wasdissolved in twice its volume of toluene and added to a solution ofgrams of technical calcium metal in 3 liters of liquid ammonia withvigorous agitation dur-- After the addition was allowed to boil ing aperiod of two hours. was complete, the ammonia to remove excess calciumand other impurities. The solvent was removed ,by heating in vacuo andthe product converted to a 50% concentrate by dissolving it in an equalweight of lubricating oil. The 50% oium had a bromine number of 45.

Example II 300 grams of cardanol was dissolved in twice its-volume oftoluene and added slowly to alsolution of 110 grams of'anhydrousstannous chloride in 2.5'liters of liquid ammonia with vigorousagitation. After the addition was complete the am monia was allowed thestannous salt of cardanol was filtered and subsequently freed of solventby heating in vacuo. The resulting tin salt was converted toa 50%concentrate by dissolving it in an equal weight of lubricating oil- Thisconcentrate analyzed 8.6% tin.

Other metal salts may be used in place of the 'stannous chloride ofExample '11 or a solution of a metal in liquid ammonia may be used ifpartialhydrogenation is desired as in Example I.

However, the phenolic composition may also be subjected to hydrogenationas, for example, with a Raney nickel catalyst under pressurev and/orreacted with other constituents to incorporate additional improvingproperties'in the form of sulfur, chlorine, nitrogen and phosphoruscontaining radicals either prior or subsequent to neutralization withmetal.

The hydrocarbon oils to which the oil-soluble metal derivatives of thepresent invention are added may be either in the crude form or partiallyor 'highly refined and may contain other additive ingredients such asdyes,- metal soaps, pour depressants, thickeners, V. I. improvers,

, oiliness agents, extreme pressure agents, sludge dispersers, hibitorssuch as sulfurized hydrocarbons, etc.

Obviously many modifications and variations of the invention, ashereinbefore set forth, may

be made without departing from the spirit and These oil-soluble metalderivatives of the pres- I ent invention may be incorporated in ahydrocarbon oil in amounts varying between 0.01 to 5.0% by weight of thefinished lubricant. The

particular proportions used depend upon the type 3 of lubricant to beimproved, the service for which the lubricant is'intended, and thedegree of improvementdesiredin the hydroearbon oil. The preferred rangeof proportions in a mineral lubricating oil wheniused in a few of, themore common services are as follows:

Per cent by weight of finished lubricant Diesel lubricating oil";...'0.5 1'.() Motor lubricating oil 0.3 -0.6 Heavy. duty lubricating oil0.5-2.5 Turbine lubricating oil .0.01-0.1 Airplane lubricating oil 0.2-0.6

The following-examples" are given a s'illustrantionsofthevvariousmethods of obtaining the oilsolublefphenolic compositions andthe preparation of the oil-soluble metal derivatives thereof:

scope thereof and, therefore, only such limita tions should be imposed aare indicated in the appended claims.

, .We claim:

1. A lubricant comprising a hydrocarbon oil and a small quantity,suilicient to impart oxidation-resistant properties to saidoil, ofanoilmiscible metal derivative of the oil-soluble phenolic compositionsderived from an oil extracted from amember of the Anacardium genus ofthe Anacardiaceae family. a

2.. A lubricant comprising a mineral lubricating oil and 0.015%-byiweight of an oil-miscible metal derivative of the oil-solublephenolic compositions derived from an oil extracted from a member of theAnacardium genus of the Ana-.

cardiaceae family 3. A lubricant comprising a hydrocarbon oil havingincorporated therein 0.015-.0% by weight of an oil-miscible metalderivativeof'the oilsoluble phenolic compositions derived from an oilextracted from a member of the Anacardium enus of the Anacardiacea efamily.

solution was filtered concentrate analyzed 3.6% calto boil on and theresidual" oxidation inhibitors, and corrosion inaasao'n 4. Alubricantcomprising a hydrocarbon bu and a smallauantity. sumcient toimpart oxidav tion-resistant properties to said 011. or an oilmisciblemetal derivative of a-partially hydrogenated oil-soluble phenoliccomposition derived from an oil extracted from a member oi theAnacardium genus of the Anacardiaceae family.

5. A lubricant comprising a'hydrocarbon oil having incorporated therein0.01 to 5.0% by weight of an (l-miscible metal derivative of a partiallyhydrogenated oil-soluble phenolic com member or the Anacardium genus ofthe Anacardiaceae family. i I

- 8. A lubricant comprising a hydrocarbon oil and a small quantity, lessthan 5% by weight, of

. an oil-soluble metalderivative or cardanol.

8. A lubricant comprising a mineral lubricat- 4 ing oil havingincorporated therein 02-15% by weight of an oil-soluble metal derivativeof cardanol.

9. A lubricant comprising a mineral lubricating oil having incorporatedtherein 02-25% by weight of an oil-soluble metal derivative of partiallyhydrogenated cardanol. i

- position derived from an oil extracted from-ca 10. A lubricantcomprising a hydrocarbon oil having incorporated therein'0.01-5.0% byweight of an oil-soluble metal derivative of a phenolic distillateobtained from the distillation oi cashew nutshell oil.

"I. A lubricant comprising a hydrocarbon oil 7 and asmall quantity, lessthan 5% by weight oi an oil-soluble metal derivative 0! partially hydro-11.-A lubricant comprising a hydrocarbon oil having incorporated therein0.01-5.0% by weight of an oil-soluble metal derivative of a partiallyhydrogenated phenolic distillate obtained from the distillation ofcashew nut shell oil,

JOHN A. PA'I'IERSONr RUSH r. mommy.

